Redox behavior of novel nickel and palladium complexes supported by trianionic non-innocent ligand containing β-diketiminate and phenol groups

Yuma Morimoto; June Takaichi; Shinichi Hanada; Kei Ohkubo; Hideki Sugimoto; Nobutaka Fujieda; Shunichi Fukuzumi; Shinobu Itoh

doi:10.1142/S1088424615500248

Redox behavior of novel nickel and palladium complexes supported by trianionic non-innocent ligand containing β-diketiminate and phenol groups

Yuma Morimoto, June Takaichi, Shinichi Hanada, Kei Ohkubo, Hideki Sugimoto, Nobutaka Fujieda, Shunichi Fukuzumi, Shinobu Itoh

Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

A new type of nickel and palladium complexes with non-innocent β-diketiminate ligand having redox active phenol groups, 2,4-di-tert-butyl-6-(((1E,2E)-3-((3,5-di-tert-butyl-2-hydroxyphenyl) amino)-2-nitroallylidene)amino)phenol (LH₃, fully protonated form) have been developed, and the structure, physical properties, and reactivity of their one-electron and two-electron oxidized complexes, [M^II(L^•2-)] and [M^II(L^-)]⁺ (M = Ni^II or Pd^II) have been examined in detail. The two-electron oxidized forms of both complexes, [M^II(L^-)]⁺, exhibited hydrogen atom abstraction ability from 1,4-cyclohexadiene (CHD) comparable to its copper analog [Cu^II(L^-)]⁺ (Dalton Trans. 2013; 42: 2438-2444). The oneelectron oxidized form of palladium complex, [Pd^II(L^•2-)], was also found to oxidize CHD, whereas the nickel analog, [Ni^II(L^•2-)], exhibited photo-induced oxidation ability of CHD.

Original language	English
Pages (from-to)	377-387
Number of pages	11
Journal	Journal of Porphyrins and Phthalocyanines
Volume	19
Issue number	1-3
DOIs	https://doi.org/10.1142/S1088424615500248
State	Published - 1 Jan 2015

Bibliographical note

Funding Information:
This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas “Molecular Activation Directed toward Straightforward Synthesis” (No. 22105007) and “Stimuli-responsive Chemical Species” (No. 24109015) and a Grant-in-Aid for Exploratory Research (No. 25620044) from the Ministry of Education, Culture, Sports, Science and Technology, Japan. Y.M., N.F., and S.I. also express their special thanks to the JSPS Japanese-German Graduate Externship Program on “Environmentally Benign Bio-and Chemical Processes” for financial support of the stay in RWTH Aachen.

Publisher Copyright:
Copyright © 2015 World Scientific Publishing Company.

Keywords

b-diketiminate ligand
nickel complex
non-innocent ligand
palladium complex

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10.1142/S1088424615500248

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@article{3de888f08786436fadae378ca4f3ee41,

title = "Redox behavior of novel nickel and palladium complexes supported by trianionic non-innocent ligand containing β-diketiminate and phenol groups",

abstract = "A new type of nickel and palladium complexes with non-innocent β-diketiminate ligand having redox active phenol groups, 2,4-di-tert-butyl-6-(((1E,2E)-3-((3,5-di-tert-butyl-2-hydroxyphenyl) amino)-2-nitroallylidene)amino)phenol (LH3, fully protonated form) have been developed, and the structure, physical properties, and reactivity of their one-electron and two-electron oxidized complexes, [MII(L•2-)] and [MII(L-)]+ (M = NiII or PdII) have been examined in detail. The two-electron oxidized forms of both complexes, [MII(L-)]+, exhibited hydrogen atom abstraction ability from 1,4-cyclohexadiene (CHD) comparable to its copper analog [CuII(L-)]+ (Dalton Trans. 2013; 42: 2438-2444). The oneelectron oxidized form of palladium complex, [PdII(L•2-)], was also found to oxidize CHD, whereas the nickel analog, [NiII(L•2-)], exhibited photo-induced oxidation ability of CHD.",

keywords = "b-diketiminate ligand, nickel complex, non-innocent ligand, palladium complex",

author = "Yuma Morimoto and June Takaichi and Shinichi Hanada and Kei Ohkubo and Hideki Sugimoto and Nobutaka Fujieda and Shunichi Fukuzumi and Shinobu Itoh",

note = "Funding Information: This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas “Molecular Activation Directed toward Straightforward Synthesis” (No. 22105007) and “Stimuli-responsive Chemical Species” (No. 24109015) and a Grant-in-Aid for Exploratory Research (No. 25620044) from the Ministry of Education, Culture, Sports, Science and Technology, Japan. Y.M., N.F., and S.I. also express their special thanks to the JSPS Japanese-German Graduate Externship Program on “Environmentally Benign Bio-and Chemical Processes” for financial support of the stay in RWTH Aachen. Publisher Copyright: Copyright {\textcopyright} 2015 World Scientific Publishing Company.",

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language = "English",

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T1 - Redox behavior of novel nickel and palladium complexes supported by trianionic non-innocent ligand containing β-diketiminate and phenol groups

AU - Morimoto, Yuma

AU - Takaichi, June

AU - Hanada, Shinichi

AU - Ohkubo, Kei

AU - Sugimoto, Hideki

AU - Fujieda, Nobutaka

AU - Fukuzumi, Shunichi

AU - Itoh, Shinobu

N1 - Funding Information: This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas “Molecular Activation Directed toward Straightforward Synthesis” (No. 22105007) and “Stimuli-responsive Chemical Species” (No. 24109015) and a Grant-in-Aid for Exploratory Research (No. 25620044) from the Ministry of Education, Culture, Sports, Science and Technology, Japan. Y.M., N.F., and S.I. also express their special thanks to the JSPS Japanese-German Graduate Externship Program on “Environmentally Benign Bio-and Chemical Processes” for financial support of the stay in RWTH Aachen. Publisher Copyright: Copyright © 2015 World Scientific Publishing Company.

PY - 2015/1/1

Y1 - 2015/1/1

N2 - A new type of nickel and palladium complexes with non-innocent β-diketiminate ligand having redox active phenol groups, 2,4-di-tert-butyl-6-(((1E,2E)-3-((3,5-di-tert-butyl-2-hydroxyphenyl) amino)-2-nitroallylidene)amino)phenol (LH3, fully protonated form) have been developed, and the structure, physical properties, and reactivity of their one-electron and two-electron oxidized complexes, [MII(L•2-)] and [MII(L-)]+ (M = NiII or PdII) have been examined in detail. The two-electron oxidized forms of both complexes, [MII(L-)]+, exhibited hydrogen atom abstraction ability from 1,4-cyclohexadiene (CHD) comparable to its copper analog [CuII(L-)]+ (Dalton Trans. 2013; 42: 2438-2444). The oneelectron oxidized form of palladium complex, [PdII(L•2-)], was also found to oxidize CHD, whereas the nickel analog, [NiII(L•2-)], exhibited photo-induced oxidation ability of CHD.

AB - A new type of nickel and palladium complexes with non-innocent β-diketiminate ligand having redox active phenol groups, 2,4-di-tert-butyl-6-(((1E,2E)-3-((3,5-di-tert-butyl-2-hydroxyphenyl) amino)-2-nitroallylidene)amino)phenol (LH3, fully protonated form) have been developed, and the structure, physical properties, and reactivity of their one-electron and two-electron oxidized complexes, [MII(L•2-)] and [MII(L-)]+ (M = NiII or PdII) have been examined in detail. The two-electron oxidized forms of both complexes, [MII(L-)]+, exhibited hydrogen atom abstraction ability from 1,4-cyclohexadiene (CHD) comparable to its copper analog [CuII(L-)]+ (Dalton Trans. 2013; 42: 2438-2444). The oneelectron oxidized form of palladium complex, [PdII(L•2-)], was also found to oxidize CHD, whereas the nickel analog, [NiII(L•2-)], exhibited photo-induced oxidation ability of CHD.

KW - b-diketiminate ligand

KW - nickel complex

KW - non-innocent ligand

KW - palladium complex

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DO - 10.1142/S1088424615500248

M3 - Article

AN - SCOPUS:84928564992

SN - 1088-4246

VL - 19

SP - 377

EP - 387

JO - Journal of Porphyrins and Phthalocyanines

JF - Journal of Porphyrins and Phthalocyanines

IS - 1-3

ER -

Redox behavior of novel nickel and palladium complexes supported by trianionic non-innocent ligand containing β-diketiminate and phenol groups

Abstract

Bibliographical note

Keywords

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